Pyridyl sulfone herbicides

ABSTRACT

Pyridyl sulfones, e.g., N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide, are useful for the regulation of plant growth and as pre-emergence and post-emergence herbicides.

RELATED APPLICATION

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 128,176, filed Apr. 24, 1980, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to pyridyl sulfones which are useful asagricultural chemicals.

French Pat. No. 1,468,747 discloses the following para-substitutedphenylsulfonamides, useful as antidiabetic agents: ##STR1## wherein R=H,halogen, CF₃ or alkyl.

Logemann et al. Chem. Abstr., 53, 18052g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR2## wherein R is butyl, phenyl or ##STR3## and R₁ is hydrogen ormethyl. When tested for hypoglycemic effect in rats (oral doses of 25mg/100 g, the compounds in which R is butyl and phenyl were most potent.

Wojciechowski, Acta Polon. Pharm. 19, p. 121-5 (1962) [Chem. Abstr., 591633e] describes the synthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)-aminocarbonyl]-4-methylbenzenesulfonamide:##STR4## Based upon similarity to a known compound, the author predictedhypoglycemic activity for the foregoing compound.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches thepreparation of compounds of Formula (i), and their use as general orselective herbicides, ##STR5## wherein R₁ and R₂ may independently bealkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

Compounds of Formula (ii), and their use as antidiabetic agents, arereported in J. Drug. Res. 6, 123 (1974). ##STR6## wherein R is pyridyl.

In U.S. Ser. No. 029,821, herbicidal compounds such asN-heterocyclic-N'(arylsulfonyl)carbamimidothioates (or compounds whereina thienyl radical is substituted for the aryl radical), such as methylN'-(2-chlorophenylsulfonyl)-N-(4-methoxy-6-methylpyrimidin-2-yl)carbamimidothioateare taught.

U.S. Pat. No. 3,689,549 to R. P. Williams discloses "heterocyclicsulfonamides wherein the heteroatoms are inert can be used, e.g.,compounds having the furan, thiophene or pyridine nucleus," in theproduction of sulfonyl isocyanates from sulfonamides in a sulfolanesolvent.

B. G. Boggiano, V. Petrow, O. Stephenson and A. M. Wild, in Journal ofPharmacy and Pharmacology 13, 567-574 (1961) disclose the followingcompounds which were tested for hypoglycemic activity. ##STR7## where##STR8## is in the 2 or 3 position.

J. Delarge in Acta Pol. Pharm. 34, 245-249 (1977) disclosesN-alkylcarbamoylpyridinesulfonamides, as described in the structurebelow, as mild anti-inflammatory agents and strong diuretics. ##STR9##R=3-, 4-, 5-, 6-Me, 2-, 4-, 6-Cl, 3-Br, 4-Et₂ N, 4-Me₂ CHNH, 4-(3-ClC₆H₄)NH, 4-(3-CF₃ C₆ H₄)NH

R'=Et, Pr, Me₂ CH, Bu ##STR10## in 2-, 3- and 4-position.

German Pat. No. 2,516,025 Nov. 6, 1975) to J. E. Delarge, C. L. Lapiereand A. H. Georges discloses the following compounds as inflammationinhibitors and diuretics. ##STR11## R=C₆ H₄ R³ (R³ =Cl, CF₃, Me, MeO, H,Br, F, NO₂, Et, NH₂), Et, iso-Pr, 4-methylfuryl, C₆ H₃ Cl₂ --, C₆ H₃(CF₃)Cl;

R'=alkylcarbamoyl, cyclohexylcarbamoyl, arylcarbamoyl, CSNHCH₂ CH═CH₂,CONHC₆ H₄ Cl-p, alkylthiocarbamoyl, H, COEt;

R² =H, Me;

X=NH, NMe, O, S, NEt; and

n=0, 1.

U.S. Pat. No. 3,346,590 (Oct. 10, 1967) (to K. Dickere and E. Kuhle)discloses the following pyridinesulfonyl isothiocyanates as novelcompounds. ##STR12##

Chem. Abstr. 83 163951p (1975) reports preparation of several3-substituted 2-alkylsulfonylpyridines: ##STR13## wherein R=CH₃ or C₂ H₅;

R¹ =SH, SR, SO₂ R or Cl; and

R² =Cl, SH or SO₂ C₂ H₅.

Compound II with R¹ =SO₂ C₂ H₅ is reported to give 96.9% inhibition ofgluconeogenesis in rat renal cortex tissue.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat, soybean and thelike. The current population explosion and concomitant world food andfiber shortage demand improvements in the efficiency of producing thesecrops. Preventing or minimizing the loss of a portion of such valuablecrops by killing or inhibiting the growth of undesired vegetation is oneway of improving this efficiency.

A wide variety of materials useful for killing or inhibiting(controlling) the growth of undesired vegetation is available; suchmaterials are commonly referred to as herbicides. The need exists,however, for still more effective herbicides that destroy or controlweeds without causing significant damage to useful crops.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula (I), toagricultural compositions containing them, and to their method-of-use asgeneral herbicides having both pre-emergence and post-emergence activityand to their use as plant growth regulants. ##STR14## wherein R is C₁-C₆ alkyl, C₃ -C₆ alkenyl, C₂ -C₄ alkoxyalkyl, C₅ -C₆ cycloalkyl,

R¹ OCH₂ CH₂ OCH₂, R¹ OCH₂ CH₂ OCH₂ CH₂, ##STR15## CF₃, CF₃ CH₂ orHGLCCF₂, HCF₂ ; R¹ is methyl or ethyl;

R² and R³ are independently H, Cl, OCH₃, F, CH₃, Br, NO₂ or CF₃ ;

n is 0, 1 or 2;

G is F, Cl, Br or CF₃ ;

L is F, Cl or H;

Z is H, F, Cl, Br, CH₃, CH₃ O or CH₃ S;

W is O or S; ##STR16## X is CH₃, CH₃ O or Cl; Y is CH₃, CH₃ CH₂, CH₃ O,CH₃ CH₂ O, CF₃ CH₂ O, CH₃ O(CH₂)_(m), CH₃ OCH₂ CH₂ O, R⁴ O₂ CR⁵ CHO,(CH₃)₂ N, CH₃ (CH₂ CN)N, NHCH₃ or NH₂ ;

E is CH, N, CCH₃, CCH₂ CH₃ or CCH₂ CH₂ Cl;

R⁴ is H, CH₃ or CH₃ CH₂ ;

R⁵ is H or CH₃ ;

R⁶ is H or CH₃ ;

m is 1 or 2;

X' is H, CH₃, CH₃ O or Cl; and

Y' is O or CH₂ ;

and their agriculturally suitable salts provided that:

(1) when W=S, then R⁶ is H; and

(2) when X=Cl, then E=CH and Y=CH₃, C₂ H₅, CH₃ O, C₂ H₅ O, CH₃O(CH₂)_(m), NH₂, NHCH₃ or N(CH₃)₂.

Preferred for reasons of their higher herbicidal activity and/or morefavorable ease of synthesis are:

(1) Compounds of Formula (I) where

R is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₂ -C₄ alkoxyalkyl, C₅ -C₆cycloalkyl, R¹ OCH₂ CH₂ OCH₂, R¹ OCH₂ CH₂ OCH₂ CH₂, ##STR17## CF₃ CH₂ orHGLCCF₂ ; R¹ is methyl or ethyl;

R² and R³ are independently H, Cl, OCH₃, F, CH₃, Br, NO₂ or CF₃ ;

n is 0, 1 or 2;

G is F, Cl, Br or CF₃ ;

L is F, Cl or H;

Z is H, F, Cl, Br, CH₃, CH₃ O or CH₃ S;

W is O or S; ##STR18## X is CH₃ or CH₃ O; Y is CH₃, CH₃ CH₂, CH₃ O, CH₃CH₂ O, CF₃ CH₂ O, CH₃ O(CH₂)_(m), CH₃ OCH₂ CH₂ O, R⁴ O₂ CR⁵ CHO, (CH₃)₂N or CH₃ (CH₂ CN)N;

E is CH, N, CCH₃, CCH₂ CH₃ or CCH₂ CH₂ Cl;

R⁴ is H, CH₃ or CH₃ CH₂ ;

R⁵ is H or CH₃ ;

R⁶ is H;

m is 1 or 2;

X' is H, CH₃, CH₃ O or Cl; and

Y' is O or CH₂ ;

and their agriculturally suitable salts.

(2) Compounds of Formula (I) or Preferred 1 wherein the substituent RSO₂is at the 2-position of the pyridine ring.

(3) Compounds of Preferred 2 wherein W is O.

(4) Compounds of Preferred 3 wherein Z is H.

(5) Compounds of Preferred 4 wherein R is C₁ -C₄ alkyl.

(6) Compounds of Preferred 5 where A is ##STR19## and E is CH or N; and

(7) Compounds of Preferred 6 wherein Y is CH₃, CH₃ O or CH₃ CH₂ O.

Specifically preferred for reasons of their highest herbicidal activityand/or most favorable ease of synthesis are:

N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide,

N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(4,6-Dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(6,7-Dihydro-4-methyl-5H-cyclopentapyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(6,7-Dihydro-4-methoxy-5H-cyclopentapyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(5,6-Dihydro-4-methylfuro[2,3-D]pyrimidin-2-yl)-aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(5,6-Dihydro-4-methoxyfuro[2,3-D]pyrimidin-2-yl)-aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide;

and

N-[(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.

DETAILED DESCRIPTION Synthesis

Pyridinesulfonyl isocyanates IV can be made by the method of Ulrich etal. [J. Org. Chem. 34, 3200 (1969)] from a suitably substitutedpyridinesulfonamide (II): ##STR20##

The sulfonamide is boiled under reflux with an excess of thionylchloride, which functions as a reactant and solvent. The reaction iscontinued until the sulfonamide protons are undetectable in the protonresonance spectrum. An overnight reaction period (about 16 hours) isfrequently sufficient, though several days (e.g. 5) may be required insome cases to convert completely the sulfonamide (II) to thethionylamide (III). Use of a dry-air or oxygen atmosphere during thereflux period can accelerate the rate of reaction of the sulfonamidewith the thionyl chloride and improve the yield in cases whereconversion in a nitrogen atmosphere is sluggish.

The thionyl chloride is evaporated and the residue treated with an inertsolvent (e.g., xylene, toluene, benzene, etc.), at least one equivalentof phosgene, and a catalytic amount of pyridine. The mixture is heatedto about 60°-140°, with 80°-100° preferred. Conversion to the isocyanateis substantially complete within about 1/4 to 3 hours. The mixturecontaining the isocyanate can be used directly for the next reactionstep [formation of compound (I), with W=O] or isolated and purified byfiltration and/or evaporation of solvent.

Compounds of Formula (I) are conveniently prepared by reacting theappropriately substituted pyridinesulfonamide with the appropriatemethyl pyrimidinylcarbamate or methyl triazinylcarbamate in the presenceof an equimolar amount of trimethylaluminum according to the procedureof reaction 2. ##STR21##

Reaction 2 is best carried out in methylene chloride at 25° to 40° for24 to 96 hours under a nitrogen atmosphere. The product is isolated byaddition of an aqueous acetic acid solution followed by extraction ofthe product into methylene chloride or direct filtration of a product oflow solubility. The product is purified by trituration with solventssuch as n-butyl chloride or ether or subjected to column chromatography.

Pyridinesulfonyl isothiocyanates VI can be made by the method of Hartke[Chem. Abstr. 64, 15783e (1966)] or U.S. Pat. No. 3,346,590 (see above):##STR22##

The sulfonamide in DMF is treated with an equivalent of carbon disulfideand two equivalents of powdered potassium hydroxide at about 35°; otherbases, including non-nucleophilic bases such as sodium hydride, can beused instead of KOH. The mixture is stirred (about 1-8 hours) untilsolution is substantially complete, then diluted with an aprotic solvent(e.g., ethyl acetate) to precipitate the intermediate potassium salt V.The latter is separated by filtration of the reaction mixture, suspendedin an inert solvent (e.g., toluene or xylene) and treated with two molesof phosgene (or thionyl chloride, etc.) at about 0°. The mixture isallowed to warm to ambient temperature, filtered and the sulfonylisothiocyanate used as-is for formation of compound (I), with W=S, orisolated by evaporation of the solvent. The sulfonyl isothiocyanates maydimerize or trimerize in some cases, but the dimers and trimers stillproduce the compound (I).

The sulfonyl isocyanate IV or isothiocyanate VI reacts with theaminoheterocyclic compound to provide the pyridyl sulfone (I): ##STR23##

This reaction is best done in an inert organic solvent (such asacetonitrile, tetrahydrofuran, methylene chloride, etc.). The reactantsmay be added in any order; the reaction is generally exothermic.Conveniently, the starting reaction temperature is ambient, but it canbe varied from about 0° to 100° if desired. The product can be isolatedby filtration if it precipitates from the reaction mixture; otherwisethe solvent can be evaporated and the residual product obtained thereby,with optional purification through trituration with an organic solvent(e.g. diethyl ether, 1-chlorobutane, etc.) in which it is only sparinglysoluble, or by recrystallization.

An alternative method for preparation of compounds (I), with W=S, is toreact sulfonamide II with a heterocyclic isothiocyanate: ##STR24##

The heterocyclic isothiocyanates used in this procedure can be made, forexample, by the method of Japan Patent Application Pub: Kokai No.51-143686, June 5, 1976, or that of W. Abraham and G. BarnikowTetrahedron 29, 691 (1973). Reaction 5 is best carried out in an inert,polar solvent (e.g., acetone or butanone) at 20° to 50°, in the presenceof a basic catalyst (e.g., K₂ CO₃ or Na₂ CO₃), during about 1 to 10hours. The alkali metal salt of (I), with W=S, is filtered off,suspended in water, and the pH adjusted down to 1-3 with acid (e.g., HClor H₂ SO₄) to form pyridyl sulfone (I), with W=S, recovered byfiltration.

The starting pyridinesulfonamides (II) can be made by one or more of theillustrative methods shown below: ##STR25## Thus, a mercaptan reactswith the chloropyridine compound in the presence of a base to form thesulfide IX, which is then oxidized to the sulfone X. ##STR26##

In reaction 7, the chloronitropyridine reacts with sodiummethanesulfinate in the presence of a solvent [preferably a polar,aprotic solvent such as N,N-dimethylformamide (DMF), dimethyl sulfoxide(DMSO), N,N-dimethylacetamide (DMAC), tetramethylenesulfone (sulfolane),etc.] at a temperature from about ambient up to the boiling point of thesolvent, to provide the sulfone XII.

Other halonitropyridines can be substituted for XI and other sulfinicacid salts for sodium methanesulfinate, depending on the particularsulfone desired. Reduction of compound XII to the amino compound XIIIcan be accomplished by conventional routes, such as with iron andaqueous acetic acid, or catalytic hydrogenation. Diazotization of theamine XIII at about -10° to 20° (preferably 0° to 10°) in the presenceof HCl and subsequent treatment with SO₂ and a copper species (such ascuprous or cupric chloride), at about -10° to 50° (preferably about 0°to 30°) produces the sulfonyl chloride XIV. Reacting the chloride XIVwith anhydrous ammonia in a solvent [e.g. tetrahydrofuran (THF),methylene chloride, butyl chloride, toluene, diethyl ether, etc.] orwith aqueous ammonia produces the sulfonamide XV; the amination can beconveniently accomplished at about -10° to 50°, with 0 to 30 preferred.

When R is haloethyl or halopropyl, the compounds (II) can be prepared asillustrated in reaction 8 for the tetrafluoroethyl compound XVIII:##STR27##

Compound XVI is described in Polish J. Chem. 52, 2041 (1978). Reactionof aminopyridinethiols with the haloalkenes occurs at 0° to 100° in aninert solvent, such as DMF, in the presence of a basic catalyst such asdiisopropylamine or potassium hydroxide. The additional steps arecarried out as described for reaction sequences 6 and 7.

When R is trifluoromethyl, the compound (II) can be made as shown:##STR28## [Ref. for similar procedure through compound XXIV: Chem.Abstr. 70, 96324c (1969)].

Thus, the methylthio compound XIX is phthaloylated by phthalic anhydridein acetic acid to compound XX, which is chlorinated photolytically tocompound XXI. Halogen exchange is accomplished with HF or SbF₃ toprepare compound XXII, which is oxidized to the sulfone XXIII, fromwhich the phthaloyl group is removed by hydrazine to provide the amineXXIV. The amino compound is converted to the sulfonamide as described inreaction sequence 7. Alternatively, the compound XXV with R astrifluoromethyl can be made as shown: ##STR29##

The chloroaminopyridine is phthaloylated as described for compound XIX.The thiol XXVII is made as mentioned for compound XVI, and thetrifluoromethylation is done as described in Chem. Abstr. 87, 134226h,with trifluoroiodomethane.

The synthesis of sulfur compounds of pyridine has been reviewed in "TheChemistry of Heterocyclic Compounds", a series published by IntersciencePubl., New York and London. Pyridinesulfonamides are described by H. L.Tale in "Pyridine and Its Derivatives" Supplement, Part 4 (1975), whichis incorporated herein by reference.

The compounds of this invention can be made by the teachings discussed,included by reference, or illustrated in the examples and tables whichfollow, wherein all parts and percentages are by weight and temperaturesare in degrees centigrade.

EXAMPLE 1 ##STR30##

A mixture of 22.1 g (0.139 mole) of 2-chloro-3-nitropyridine, 14.5 g(0.142 mole) of sodium methanesulfinate and 150 ml of DMF was boiledunder reflux for 1 hour. The DMF was evaporated in vacuum and theresidue extracted with ethyl acetate. The ethyl acetate extract waswashed with water, dilute brine and saturated brine, dried (MgSO₄) andevaporated in vacuum to an oil. The oil was crystallized from butylchloride and the solid twice recrystallized from acetone/hexane toprovide 9.1 g of the sulfone XII as a tan solid, m.p. 104°-107°.##STR31##

A solution of 9.68 g (0.0479 mole) of the sulfone XII in 50 ml of aceticacid was treated with 12.5 ml of water, then, portionwise with 11.5 g ofpowdered iron. The temperature was kept at ≦95° during the exothermicreaction by periodic cooling. After an additional 10 minutes at about83° the mixture was filtered, the filtrate diluted with water and the pHraised to about 6 by gradual addition of 50% NaOH, with cooling to ≦25°;the solution was then evaporated to dryness in vacuum. The residue wastreated with ethyl acetate and sodium bicarbonate, the ethyl acetatesolution dried (MgSO₄), filtered, and evaporated to 7.41 g of a syrup,which was the amine XIII. Mass spectral analysis of the syrup showed theexpected molecular ion, m/e 172, for amine XIII. ##STR32##

A solution of 6.73 g (0.0391 mole) of the aminopyridyl sulfone XIII in 9ml of acetic acid was added to 29 ml of cold conc. HCl at 0° to 10°. Thesolution was treated, portionwise, at 0° to 5°, with a solution of 3.83g of sodium nitrite in 10.2 ml of water, with development of an orangecolor. After an additional 15 minutes at this temperature, the diazoniummixture was added, in portions, to a stirred mixture of 1.1 g of cuprouschloride, 8 ml (liquid) of sulfur dioxide and 42 ml of acetic acid at 5°to 15°; gas evolution occurred rapidly throughout the addition. After anadditional 15 minutes, the mixture was warmed to 25°, and the resultingmixture poured into excess ice water. Precipitated white solid wasfiltered off, washed with water, and dried, providing 5.26 g of thesulfonyl chloride XIV as a white solid, m.p. 162°-163° (dec.). ##STR33##

The sulfonyl chloride XIV obtained in Part c was dissolved in THF,cooled in an ice bath and gassed with ammonia, with a resultingexothermic reaction along with the precipitation of a white solid. Themixture was evaporated in vacuum to a white solid, which was washed withwater to remove ammonium chloride, leaving the sulfonamide XV as a whitesolid, m.p. 195°-196.5°. Mass spectral analysis of the solid showed amolecular ion m/e 237 (m+1). ##STR34##

One gram (0.00423 mole) of the sulfonamide XV was suspended in 100 ml ofthionyl chloride. The mixture was boiled under reflux for about 3 days,dissolution of the sulfonamide occurring in 10-15 minutes. The solutionwas evaporated to a clear, brown oil (XXVIII). An excess of solution ofphosgene in toluene (13.8% phosgene solution) was added along with 3-4drops of pyridine. The mixture was heated at 85° under phosgene refluxfor 2 hours, cooled, and filtered. The filtrate was evaporated to asolid (XXIX), which showed a strong isocyanate absorption peak in theinfrared spectrum (ca. 2250 cm⁻¹, nujol mull).

The solid isocyanate was dissolved in a little acetonitrile and treatedwith 0.5 g of 2-amino-4,6-dimethylpyrimidine, a reaction quicklyoccurring with precipitation of white solid. After a few minutes themixture was filtered and the white solid washed with acetonitrile andbutyl chloride, leaving 0.71 g of the pyridyl sulfone XXX as a whitesolid, m.p. 234° (dec.). Mass spectral analysis ##STR35##

Anal. Calcd. for XXX, C₁₃ H₁₅ N₅ O₅ S₂ (M.W. 385.42): C, 40.5; H, 3.9;N, 18.2. Anal. Found: C, 40.8; H, 4.0; N. 18.5.

                                      TABLE I                                     __________________________________________________________________________     ##STR36##                                                                    RSO.sub.2        Z    W R.sup.6                                                                          A                                                  __________________________________________________________________________    2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR37##      m.p. 229° dec.              2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR38##      m.p. 223° dec.              2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR39##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR40##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR41##      m.p. 185° dec.              2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR42##      m.p. 187° dec.              2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR43##      m.p. 209° dec.              2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR44##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR45##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR46##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR47##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR48##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR49##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR50##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR51##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR52##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR53##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR54##                                         2-CH.sub. 3 SO.sub.2                                                                           H    O H                                                                                 ##STR55##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR56##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR57##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR58##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR59##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR60##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR61##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR62##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR63##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR64##      m.p. 218-220°               2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR65##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR66##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR67##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR68##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR69##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR70##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR71##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR72##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR73##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR74##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR75##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR76##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR77##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR78##                                         2-CH.sub.3 SO.sub. 2                                                                           H    O H                                                                                 ##STR79##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR80##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR81##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR82##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR83##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR84##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR85##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR86##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR87##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR88##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR89##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR90##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR91##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR92##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR93##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR94##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR95##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR96##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR97##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR98##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR99##                                         2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR100##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR101##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR102##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR103##                                        2-CH.sub.3 SO.sub.2                                                                            6-Cl O H                                                                                 ##STR104##                                        2-CH.sub.3 SO.sub.2                                                                            6-Br O H                                                                                 ##STR105##                                        2-CH.sub.3 SO.sub.2                                                                            6-F  O H                                                                                 ##STR106##                                        2-CH.sub.3 SO.sub.2                                                                            6-CH.sub.3                                                                         O H                                                                                 ##STR107##                                        2-CH.sub.3 SO.sub.2                                                                            6-CH.sub.3 O                                                                       O H                                                                                 ##STR108##                                        2-CH.sub.3 SO.sub.2                                                                            6-CH.sub.3 S                                                                       O H                                                                                 ##STR109##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR110##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR111##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR112##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR113##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR114##                                        2-CH.sub.3 SO.sub.2                                                                            H    S H                                                                                 ##STR115##                                        2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR116##     m.p. 194-196°               2-CH.sub.3 (CH.sub.2).sub.5 SO.sub.2                                                           H    O H                                                                                 ##STR117##                                        2-CH.sub.2CHCH.sub.2 SO.sub.2                                                                  H    O H                                                                                 ##STR118##                                        2-CH.sub.3 (CH.sub.2).sub.2 CHCHCH.sub.2 SO.sub.2                                              H    O H                                                                                 ##STR119##                                        2-CH.sub.3 OCH.sub.2 SO.sub.2                                                                  H    O H                                                                                 ##STR120##                                        2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 SO.sub.2                                                  H    O H                                                                                 ##STR121##                                        2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                               H    O H                                                                                 ##STR122##                                        2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                        H    O H                                                                                 ##STR123##                                        2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                      H    O H                                                                                 ##STR124##                                        2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                               H    O H                                                                                 ##STR125##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR126##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR127##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR128##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR129##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR130##                                        4-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR131##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR132##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR133##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR134##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR135##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR136##                                        5-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR137##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR138##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR139##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR140##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR141##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR142##                                        6-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR143##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR144##                                         ##STR145##      H    O H                                                                                 ##STR146##                                         ##STR147##      H    O H                                                                                 ##STR148##                                         ##STR149##      H    O H                                                                                 ##STR150##                                         ##STR151##      H    O H                                                                                 ##STR152##                                         ##STR153##      H    O H                                                                                 ##STR154##                                         ##STR155##      H    O H                                                                                 ##STR156##                                         ##STR157##      H    O H                                                                                 ##STR158##                                         ##STR159##      H    O H                                                                                 ##STR160##                                         ##STR161##      H    O H                                                                                 ##STR162##                                         ##STR163##      H    O H                                                                                 ##STR164##                                         ##STR165##      H    O H                                                                                 ##STR166##                                         ##STR167##      H    O H                                                                                 ##STR168##                                         ##STR169##      H    O H                                                                                 ##STR170##                                         ##STR171##      H    O H                                                                                 ##STR172##                                         ##STR173##      H    O H                                                                                 ##STR174##                                        2-CF.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR175##                                        2-HCF.sub.2 CF.sub.2 SO.sub.2                                                                  H    O H                                                                                 ##STR176##                                        2-HCFClCF.sub.2 SO.sub.2                                                                       H    O H                                                                                 ##STR177##                                        2-HCF.sub.2 SO.sub.2                                                                           H    O H                                                                                 ##STR178##                                        2-HCFBrCF.sub.2 SO.sub.2                                                                       H    O H                                                                                 ##STR179##                                        2-CF.sub.3 HCFCF.sub.2 SO.sub.2                                                                H    O H                                                                                 ##STR180##                                        2-HCCl.sub.2 CF.sub.2 SO.sub.2                                                                 H    O H                                                                                 ##STR181##                                        2-H.sub.2 CFCF.sub.2 SO.sub.2                                                                  H    O H                                                                                 ##STR182##                                        2-CF.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR183##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR184##     m.p. 211-212°               2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR185##                                        2-CH.sub.3 SO.sub.2                                                                            H    O H                                                                                 ##STR186##                                        2-CH.sub.3 SO.sub.2                                                                            H    O CH.sub.3                                                                          ##STR187##                                        2-CH.sub.3 SO.sub.2                                                                            H    O CH.sub.3                                                                          ##STR188##                                        2-CH.sub.3 SO.sub.2                                                                            H    O CH.sub.3                                                                          ##STR189##                                        2-CH.sub.3 SO.sub.2                                                                            H    O CH.sub.3                                                                          ##STR190##                                        2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR191##     m.p. 205-209°               2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR192##     m.p. 197-200°               2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR193##     m.p. 209-211°               2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR194##     m.p. 199-201°               2-CH.sub.3 CH.sub.2 SO.sub.2                                                                   H    O H                                                                                 ##STR195##     m.p. 176-179°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR196##     m.p. 200-202°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR197##     m.p. 195-198°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR198##     m.p. 187-192°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR199##     m.p. 196-198°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR200##     m.p. 183-185°               2-(CH.sub.3).sub.2 CHSO.sub.2                                                                  H    O H                                                                                 ##STR201##     m.p. 182-184°               2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR202##     m.p. 168-172°               2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR203##     m.p. 170-174°               2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR204##     m.p. 208-211°               2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR205##     m.p. 172-174.5°             2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR206##     m.p. 178-183°               2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                          H    O H                                                                                 ##STR207##     m.p. 181-185°               __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                         ##STR208##                                                                   RSO.sub.2                Z                                                    ______________________________________                                        2-C.sub.2 H.sub.5 SO.sub.2                                                                             H                                                    2-CH.sub.3 (CH.sub.2).sub.5 SO.sub.2                                                                   H                                                    2-CH.sub.2CHCH.sub.2 SO.sub.2                                                                          H                                                    2-CH.sub.3 (CH.sub.2).sub.2 CHCHCH.sub.2 SO.sub.2                                                      H                                                    2-CH.sub.3 OCH.sub.2 SO.sub.2                                                                          H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 SO.sub.2                                                          H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                       H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                              H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                       H                                                    2-CH.sub.3 SO.sub.2      6-Cl                                                 2-CH.sub.3 SO.sub.2      6-Br                                                 2-CH.sub.3 SO.sub.2      6-F                                                  2-CH.sub.3 SO.sub.2      6-CH.sub.3                                           2-CH.sub.3 SO.sub.2      6-CH.sub.3 O                                         2-CH.sub.3 SO.sub.2      6-CH.sub.3 S                                         4-CH.sub. 3 SO.sub.2     H                                                    5-CH.sub.3 SO.sub.2      H                                                    6-CH.sub.3 SO.sub.2      H                                                     ##STR209##              H                                                     ##STR210##              H                                                     ##STR211##              H                                                     ##STR212##              H                                                     ##STR213##              H                                                     ##STR214##              H                                                     ##STR215##              H                                                     ##STR216##              H                                                     ##STR217##              H                                                     ##STR218##              H                                                     ##STR219##              H                                                     ##STR220##              H                                                     ##STR221##              H                                                     ##STR222##              H                                                     ##STR223##              H                                                    2-CF.sub.3 SO.sub.2      H                                                    2-HCF.sub.2 CF.sub.2 SO.sub.2                                                                          H                                                    2-HCFClCF.sub.2 SO.sub.2 H                                                    2-HCFBrCF.sub.2 SO.sub.2 H                                                    2-CF.sub.3 HCFCF.sub.2 SO.sub.2                                                                        H                                                    2-HCCl.sub.2 CF.sub.2 SO.sub.2                                                                         H                                                    2-H.sub.2 CFCF.sub.2 SO.sub.2                                                                          H                                                    2-CF.sub.3 CH.sub.2 SO.sub.2                                                                           H                                                    2-HCF.sub.2 SO.sub.2     H                                                    ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR224##                                                                   RSO.sub.2          Z                                                          ______________________________________                                        2-C.sub.2 H.sub.5 SO.sub.2                                                                       H         m.p. 176-177°                             2-CH.sub.3 (CH.sub.2).sub.5 SO.sub.2                                                             H                                                          2-CH.sub.2CHCH.sub.2 SO.sub.2                                                                    H                                                          2-CH.sub.3 (CH.sub.2).sub.2 CHCHCH.sub.2 SO.sub.2                                                H                                                          2-CH.sub.3 OCH.sub.2 SO.sub.2                                                                    H                                                          2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 SO.sub.2                                                    H                                                          2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                 H                                                          2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                          H                                                          2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                        H                                                          2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                 H                                                          2-CH.sub.3 SO.sub.2                                                                              6-Cl                                                       2-CH.sub.3 SO.sub.2                                                                              6-Br                                                       2-CH.sub.3 SO.sub.2                                                                              6-F                                                        2-CH.sub.3 SO.sub.2                                                                              6-CH.sub.3                                                 2-CH.sub.3 SO.sub.2                                                                              6-CH.sub.3 O                                               2-CH.sub.3 SO.sub.2                                                                              6-CH.sub.3 S                                               4-CH.sub.3 SO.sub.2                                                                              H                                                          5-CH.sub.3 SO.sub.2                                                                              H                                                          6-CH.sub.3 SO.sub.2                                                                              H                                                           ##STR225##        H                                                           ##STR226##        H                                                           ##STR227##        H                                                           ##STR228##        H                                                           ##STR229##        H                                                           ##STR230##        H                                                           ##STR231##        H                                                           ##STR232##        H                                                           ##STR233##        H                                                           ##STR234##        H                                                           ##STR235##        H                                                           ##STR236##        H                                                           ##STR237##        H                                                           ##STR238##        H                                                           ##STR239##        H                                                          2-CF.sub.3 SO.sub.2                                                                              H                                                          2-HCF.sub.2 CF.sub.2 SO.sub.2                                                                    H                                                          2-HCFClCF.sub.2 SO.sub.2                                                                         H                                                          2-HCFBrCF.sub.2 SO.sub.2                                                                         H                                                          2-CF.sub.3 HCFCF.sub.2 SO.sub.2                                                                  H                                                          2-HCCl.sub.2 CF.sub.2 SO.sub.2                                                                   H                                                          2-H.sub.2 CFCF.sub.2 SO.sub.2                                                                    H                                                          2-CF.sub.3 CH.sub.2 SO.sub.2                                                                     H                                                          2-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                            H         m.p. 118-120.5°                           2-(CH.sub.3).sub.2 CHSO.sub.2                                                                    H         m.p. 132-134°                             2-HCF.sub.2 SO.sub.2                                                                             H                                                          ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                         ##STR240##                                                                   RSO.sub.2                Z                                                    ______________________________________                                        2-C.sub.2 H.sub.5 SO.sub.2                                                                             H                                                    2-CH.sub.3 (CH.sub.2).sub.5 SO.sub.2                                                                   H                                                    2-CH.sub.2CHCH.sub.2 SO.sub.2                                                                          H                                                    2-CH.sub.3 (CH.sub.2).sub.2 CHCHCH.sub.2 SO.sub.2                                                      H                                                    2-CH.sub.3 OCH.sub.2 SO.sub.2                                                                          H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 SO.sub.2                                                          H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                       H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                              H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                       H                                                    2-CH.sub.3 SO.sub.2      6-Cl                                                 2-CH.sub.3 SO.sub.2      6-Br                                                 2-CH.sub.3 SO.sub.2      6-F                                                  2-CH.sub.3 SO.sub.2      6-CH.sub.3                                           2-CH.sub.3 SO.sub.2      6-CH.sub.3 O                                         2-CH.sub.3 SO.sub.2      6-CH.sub.3 S                                         4-CH.sub. 3 SO.sub.2     H                                                    5-CH.sub.3 SO.sub.2      H                                                    6-CH.sub.3 SO.sub.2      H                                                     ##STR241##              H                                                     ##STR242##              H                                                     ##STR243##              H                                                     ##STR244##              H                                                     ##STR245##              H                                                     ##STR246##              H                                                     ##STR247##              H                                                     ##STR248##              H                                                     ##STR249##              H                                                     ##STR250##              H                                                     ##STR251##              H                                                     ##STR252##              H                                                     ##STR253##              H                                                     ##STR254##              H                                                     ##STR255##              H                                                    2-CF.sub.3 SO.sub.2      H                                                    2-HCF.sub.2 CF.sub.2 SO.sub.2                                                                          H                                                    2-HCFClCF.sub.2 SO.sub.2 H                                                    2-HCFBrCF.sub.2 SO.sub.2 H                                                    2-CF.sub.3 HCFCF.sub.2 SO.sub.2                                                                        H                                                    2-HCCl.sub.2 CF.sub.2 SO.sub.2                                                                         H                                                    2-H.sub.2 CFCF.sub.2 SO.sub.2                                                                          H                                                    2-CF.sub.3 CH.sub.2 SO.sub.2                                                                           H                                                    2-HCF.sub.2 SO.sub.2     H                                                    ______________________________________                                    

                  TABLE V                                                         ______________________________________                                         ##STR256##                                                                   RSO.sub.2                Z                                                    ______________________________________                                        2-CH.sub.3 SO.sub.2      H                                                    2-C.sub.2 H.sub.5 SO.sub.2                                                                             H                                                    2-CH.sub.3 (CH.sub.2).sub.5 SO.sub.2                                                                   H                                                    2-CH.sub.2CHCH.sub.2 SO.sub.2                                                                          H                                                    2-CH.sub.3 (CH.sub.2).sub.2 CHCHCH.sub.2 SO.sub.2                                                      H                                                    2-CH.sub.3 OCH.sub.2 SO.sub.2                                                                          H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 SO.sub.2                                                          H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                       H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2                                                H                                                    2-CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                              H                                                    2-C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2                                       H                                                    2-CH.sub.3 SO.sub.2      6-Cl                                                 2-CH.sub.3 SO.sub.2      6-Br                                                 2-CH.sub.3 SO.sub.2      6-F                                                  2-CH.sub.3 SO.sub.2      6-CH.sub.3                                           2-CH.sub.3 SO.sub.2      6-CH.sub.3 O                                         2-CH.sub.3 SO.sub. 2     6-CH.sub.3 S                                         4-CH.sub.3 SO.sub.2      H                                                    5-CH.sub.3 SO.sub.2      H                                                    6-CH.sub.3 SO.sub.2      H                                                     ##STR257##              H                                                     ##STR258##              H                                                     ##STR259##              H                                                     ##STR260##              H                                                     ##STR261##              H                                                     ##STR262##              H                                                     ##STR263##              H                                                     ##STR264##              H                                                     ##STR265##              H                                                     ##STR266##              H                                                     ##STR267##              H                                                     ##STR268##              H                                                     ##STR269##              H                                                     ##STR270##              H                                                     ##STR271##              H                                                    2-CF.sub.3 SO.sub.2      H                                                    2-HCF.sub.2 CF.sub.2 SO.sub.2                                                                          H                                                    2-HCFClCF.sub.2 SO.sub.2 H                                                    2-HCFBrCF.sub.2 SO.sub.2 H                                                    2-CF.sub.3 HCFCF.sub.2 SO.sub.2                                                                        H                                                    2-HCCl.sub.2 CF.sub.2 SO.sub.2                                                                         H                                                    2-H.sub.2 CFCF.sub.2 SO.sub.2                                                                          H                                                    2-CF.sub.3 CH.sub.2 SO.sub.2                                                                           H                                                    2-HCF.sub.2 SO.sub.2     H                                                    ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula (I) can be prepared inconventional ways. They include dusts, granules, pellets, suspensions,emulsions, wettable powders, emulsifiable concentrates and the like.Many of them can be applied directly. Sprayable formulations can beextended in suitable media and used at spray volumes of from a fewliters to several hundred liters per hectare. The formulations, broadly,contain about 0.1% to 99% by weight of active ingredient(s) and at leastone of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9%solid or liquid diluent(s). More specifically, they will contain theseingredients in the approximate proportions set forth in Table VI.

                  TABLE VI                                                        ______________________________________                                                   Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                    ______________________________________                                        Wettable Powders                                                                           20-90      0-74      1-10                                        Oil Suspensions,                                                                            3-50     40-95      0-15                                        Solutions,                                                                    Emulsions (in-                                                                cluding Emulsi-                                                               fiable Concen-                                                                trates)                                                                       Aqueous Suspensions                                                                        10-50     40-84      1-20                                        Dusts         1-25     70-99     0-5                                          Granules and 0.1-95      5-99.9   0-15                                        Pellets                                                                       ______________________________________                                         *Active Ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation, or bytank mixing.

Some typical solid diluents are described in Watkins, et al., "Handbookof Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates,solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending, and usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material on preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7,line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192 Col. 5, line 43 through Col.7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140,162-164, 166, 167 and 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Col. 3, line 66 throughCol. 5., line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

Unless indicated otherwise, all parts are by weight in the followingexamples.

EXAMPLE 2

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          95%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        dioctyl sodium sulfosuccinate                                                                              0.1%                                             sodium ligninsulfonate       1%                                               synthetic fine silica        3.9%                                             ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles almost all of which are below 100 microns in size. Thatmaterial is sifted through a U.S.S. No. 50 screen and packaged.

EXAMPLE 3

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          40%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        dioctyl sodium sulfosuccinate                                                                              1.5%                                             sodium ligninsulfonate       3%                                               low-viscosity methyl cellulose                                                                             1.5%                                             attapulgite                  54%                                              ______________________________________                                    

The ingredients are thoroughly blended and passed through an air mill toproduce an average particle size under 15 microns, reblended, and siftedthrough a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

EXAMPLE 4

    ______________________________________                                        Granule                                                                       ______________________________________                                        wettable powder of Example 3                                                                       25%                                                      gypsum               64%                                                      potassium sulfate    11%                                                      ______________________________________                                    

The ingredients are blended in a rotating mixer, and water is sprayedonto that blend so as to effect granulation. When most of the granuleshave reached 1.0 to 0.42 mm (U.S.S. #18 to 40 sieves) in size, they areremoved, dried, and screened. Oversize material is crushed to produceadditional material in the desired range. The resulting granules contain10% of the active ingredient.

EXAMPLE 5

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          65%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        dodecylphenol polyethylene glycol                                                                          2%                                               ether                                                                         sodium ligninsulfonate       4%                                               sodium silicoaluminate       6%                                               montmorillonite (calcined)   23%                                              ______________________________________                                    

The ingredients are thoroughly blended. The liquid surfactant is addedby spraying on the solid ingredients in a blender. After grinding in ahammer-mill to produce particles almost all of which are below 100microns in size, the material is reblended, sifted through a U.S.S. #50sieve (0.3 mm opening) and packaged.

EXAMPLE 6

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          25%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        polyoxyethylene sorbitol hexaoleate                                                                        5%                                               highly aliphatic hydrocarbon oil                                                                           70%                                              ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingsuspension may be applied directly, but preferably after being extendedfurther with oils or emulsified in water.

EXAMPLE 7

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                         25%                                               (methylsulfonyl)-3-pyridinesulfonamide                                        hydrated attapulgite        3%                                                crude calcium ligninsulfonate                                                                             10%                                               sodium dihydrogen phosphate 0.5%                                              water                       61.5%                                             ______________________________________                                    

The ingredients are ground together in a ball or roller mill until thesolid particles have been reduced to sizes under 10 microns, and thenpackaged.

EXAMPLE 8

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          25%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        anhydrous sodium sulfate     10%                                              crude calcium ligninsulfonate                                                                              5%                                               sodium alkylnaphthalenesulfonate                                                                           1%                                               calcium/magnesium bentonite  59%                                              ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about12% water. The mixture is extruded in the form of cylinders about 3 mmin diameter which are cut to produce pellets about 3 mm long. Thepellets may be used directly, after drying, or dried pellets may becrushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granulesheld on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for useand the fines recycled.

EXAMPLE 9

    ______________________________________                                        Solution                                                                      ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          5%                                               (methylsulfonyl)-3-pyridinesulfonamide                                        dimethylformamide            95%                                              ______________________________________                                    

The ingredients are combined and stirred to produce a solution, whichcan be used for low-volume applications.

EXAMPLE 10

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          80%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        sodium alkylnaphthalenesulfonate                                                                           2%                                               sodium ligninsulfonate       2%                                               synthetic amorphous silica   3%                                               kaolinite                    13%                                              ______________________________________                                    

The ingredients are thoroughly blended after grinding in a hammer millto produce particles essentially all of which are under 100 microns insize; the material is reblended, sifted through a U.S.S. No. 50 sieveand packaged.

EXAMPLE 11

    ______________________________________                                        N--[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          80%                                              (methylsulfonyl)-3-pyridinesulfonamide                                        wetting agent                1%                                               crude ligninsulfonate salt (con-                                                                           10%                                              taining 5-20% of the natural                                                  sugars)                                                                       attapulgite clay             9%                                               ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

Utility

The compounds of the present invention are superior herbicides. Theyhave utility for broad-spectrum pre- and/or post-emergence weed controlin areas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,parking lots, drive-in theaters, around billboards, highway and railroadstructures.

The rates of application for the compounds of the invention aredetermined by a number of factors, including the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.05 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for situations where onlyshort-term persistence is required, or for use as plant growthmodifiers.

The compounds of the invention may be used in combination with any othercommercial herbicide, examples of which are those of the triazine,triazole, uracil, urea, amide, diphenyl ether, carbamate andbipyridylium types.

The herbicidal and growth modifying properties of the subject compoundswere discovered in a number of greenhouse tests. The test procedures andresults follow.

Test Procedure A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), Cassia tora, morningglory (Ipomoeaspp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, wheat aswell as nutsedge tubers were planted in a growth medium and treatedpreemergence with the chemicals dissolved in a non-phytotoxic solvent.At the same time, cotton having five leaves (including cotyledonaryones), bush beans with the third trifoliolate leaf expanding, crabgrass,barnyardgrass and wild oats with two leaves, cassia with three leaves(including cotyledonary ones), morningglory and cocklebur with fourleaves (including the cotyledonary ones), sorghum and corn with fourleaves, soybean with two cotyledonary leaves, rice with three layers,wheat with one leaf, and nutsedge with three-five leaves were sprayed.Treated plants and controls were maintained in a greenhouse for sixteendays, whereupon all species were compared to controls and visually ratedfor response to treatment. The ratings are based on a numerical scaleextending from 0=no injury, to 10=complete kill. The accompanyingdescriptive symbols have the following meanings:

C=chlorosis/necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

S=albinism;

U=unusual pigmentation;

X=axillary stimulation; and

6Y=abscised buds or flowers.

The ratings for the compounds tested by this procedure are presented inTable A.

    TABLE A      POST- EMERGENCE           Barn-  Morn-      Rate Bush-  Sorg-    Wild     yard- Crab- ing Cock-  Nut- Sugar-  (kg/ha) bean Cotton hum Corn Soybean     Wheat Oats Rice grass grass Glory lebur Cassia sedge beets      ##STR272##      0.4 5C, 9G, 6Y 9C 9C 5U, 9G 9C 5C, 8G 7C 5C, 7G 7C, 9H 9C 10C 9C 5C, 8G     8G      Compound 1     ##STR273##      0.05 5C, 9G, 6Y 4C, 8G 2C, 8G 4U, 9C 4G 2C, 9G 2C, 8G 5C, 9G 3C, 9H 2C     2C, 5H 3C, 8H 2C, 5G 5G 2C, 8G      Compound 2     ##STR274##      0.4 9C 10C 6C, 9G 6C, 9G 9C 6C, 9G 6C, 9G 5C, 9G 9C 9C 10C 10C 9C 5C,     9G 5C, 9G      Compound 2     ##STR275##      0.05 9C 6C, 9G 5C, 9G 3C, 9G 4C, 9G 4C, 9G 4C, 9G 4C, 9G 9C 3C, 9G 9C     10C 9C 9G      Compound 3     ##STR276##      0.05 5S, 9G, 6Y -- 2C, 9G 5C, 9H 0 0 2C, 7G 5C, 9G 2C, 8H 2C, 5G 2C 1C     1C 0      Compound 4     ##STR277##      0.05 9D, 9G, 6Y 5C, 9G 9C 4C, 9G 2C, 7G 6C, 9G 5C, 9G 5C, 9G 5C, 9H 4C,     8G 5C, 9G 9C 9C 10C      Compound 5     ##STR278##      0.4 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C      Compound 5     ##STR279##      0.05 9C 5C, 9G 9C 9C 5C, 9G 2C, 9H 2C, 9H 5C, 9G 9C 2C, 8G 3C, 7G 9C 9C     2C, 8G      Compound 6     ##STR280##      0.05 9C -- 2C, 9G 6C, 9G 2C, 7G 9C 2C, 9G 3C, 9G 2C, 9H 2C, 5G 3C, 7H     4C, 8H 3C, 5H 1C      Compound 7     ##STR281##      0.05 9C 5C, 9G 9C 4C, 9G 2C, 9H 5U, 9G 5C, 9G 5C, 9G 9C 5C, 9G 5C, 9G     9C 5C, 9G 3C, 9G 5C, 9H      Compound 8     ##STR282##      0.05 5C, 9G, 6Y 6C, 9G 9C 9C 5C, 9G 9C 9C 5C, 9G 9C 5C, 9G 5C, 9H 10C     9C 2C, 9G 9C      Compound 9     ##STR283##      0.05 9C 9C 9C 10C 9C 9C 9C 9C 9C 9C 2C, 7G 10C 9C 10C 9C  Compound 10      ##STR284##      0.05 3C, 3H, 6Y 2C 2U, 9G 5U, 9G 1B, 3G 2C, 9G 6G 4C, 9G 2C, 9H 3G 1C,     1H 4G 2G 5G 2G      Compound 11     ##STR285##      0.05 6C, 9G, 6Y 4C, 8G 3U, 9C 10C 3C, 8H 9C 2C, 8G 6C, 9G 9C 2C, 9G 3C,     6G 2H, 8G 3C, 7H 8G 4C, 9H      Compound 12     ##STR286##      0.05 5C, 9G, 6Y 5C, 8G 4U, 9C 9C 3C, 8H 5C, 9G 5C, 9G 5C, 9G 5C, 9H 5C,     9H 2C, 7G 3C, 9H 3C, 7H 6G 5C, 9G      Compound 13     ##STR287##      0.05 5G, 6Y 4C, 5H 3C, 9G 2C, 5H 1H 5G 6G 9G 2C, 9H 3G 4C, 8G 3C, 8H 3C     2G 3C, 9H      Compound 14     ##STR288##      0.05 3C, 9G, 6Y 2C, 8G 3C, 9G 3U, 9G 3C, 9G, 5X 2U, 9G 3C, 9G 5C, 9G 9C     3C, 9G 6C, 9G 9C 4C, 9G 3C, 9G 5C, 9G      Compound 15     ##STR289##      0.05 9C 4C, 9G 9C 5U, 9G 4C, 9G 6C, 9G 5C, 9G 5C, 9G 9C 5C, 9G 9C 10C     6C, 9G 5C, 9G 9C      Compound 16     ##STR290##      0.05 1H 2C 1C, 4H 2C, 6H 2G 0 0 8G 1C, 2H 0 0 0 0 4G 0  Compound 17      ##STR291##      0.05 4C, 7G, 6Y 3C, 4G 5C, 9G 6C, 9G 4H 3C, 9G 3C, 9G 5C, 9G 9C 3C, 7G     3C, 5G 3C, 8H 3C, 7G 5G 2C, 2H      Compound 18     ##STR292##      0.05 2C, 3G, 6Y 2C, 3H 5C, 9G 5U, 9C 3H, 5G, 7X 5C, 9G 4C, 9H 5C, 9G     5C, 9H 3C, 8G 3C, 8G 3C, 7G 3C, 5G 5G 3C, 5H      Compound 19     ##STR293##       .05 3C, 9G, 6Y 5C, 9G 9C 9C 4H, 8G 2C, 7G 8G 9C 5C, 9H 4C, 9H 8G 10C     5C, 9G 5C, 9G 9C      Compound 20     ##STR294##       .5 9C 6C, 9G 10C 10C 9C 9C 10C 8C 9C 9C 3C, 9G 9C 9C 9C --  Compound     21      ##STR295##       .5 9C 6C, 9G 9C 7U,10C 9C 9C 9C 6C, 9G 9C 9C 6C, 9G 9C 9C 4C, 5G --     Compound 22      ##STR296##       .5 2C 1C 2C, 8G 3U, 7G 2G 2C, 6G 1C, 5G 2C, 6G 2C, 6H 4C, 5G 0 0 1C 0     --      Compound 23     ##STR297##       .5 5C, 9G, 6Y 2C, 3H, 5G 9C 8U, 9C 1C, 2H, 5G 5U, 9C 9C 6C, 9G 9C 2C,     8G 2C, 4G 1C, 2H 1C, 4G 2G --      Compound 24     ##STR298##       .5 9D, 9G, 6Y 2C, 2H, 5G 10C 8U, 9C 3C, 8H 9C 9C 9C 9C 3C, 7G 2C, 6G     2C, 5H 2C, 3H 2C, 7G      Compound 25     ##STR299##       .05 3C, 9G, 6Y 3C, 3H, 9G 5C, 9G 4U, 9G 2C, 7G, 5X 2C, 9G 2C, 9G 5C,     9G 9C 2C, 9H 0 5G 3C, 3H 7G --      Compound 26     ##STR300##       .05 6C, 9G, 6Y 5C, 9G 3C, 9G 9C 3C, 9G 9C 9C 5C, 9G 2C, 8H 2C, 8G 1C     4C, 9G 2C, 5G 0 --        PRE-EMERGENCE         Barn-  Morn-     Rate Sorg-    Wild  yard-     Crab- ing Cock-  Nut- Sugar- (kg/ha) hum Corn Soybean Wheat Oats Rice     grass grass Glory lebur Cassia sedge beets      ##STR301##      0.4 5C, 9H 9H 9H 9H 3C, 8H 10E 9H 2C, 9G 9G 9H 9G 10E  Compound 1      ##STR302##      0.05 4C, 9G 4C, 9H 1C 2C, 9G 4C, 9H 9H 2C 0 5H 2C, 3H 1C 0 4C, 6G     Compound 2      ##STR303##      0.4 5C, 9H 9H 9H 9H 5C, 9H 10E 5C, 9H 5C, 9G 9C 9H 9G 10E  Compound 2      ##STR304##      0.05 5C, 9H 9G 9H 2C, 9H 3C, 9H 10E 2C, 9H 3C, 8G 9G -- 9G 10E     Compound 3      ##STR305##      0.05 3C, 6G 2C, 5G 0 0 0 2C, 6H 0 3G 2G 0 2C 0      Compound 4     ##STR306##      0.05 8C, 9H 9H 2C, 5H 9H 3C, 8H 10E 9H, 2C 3C, 8G 8G 9H 8G 9G  Compound     5      ##STR307##      0.4 10H 10H 9H 9H 5C, 9H 10E 5C, 9H 10E 9G 9H 10C 10E  Compound 5      ##STR308##      0.05 2C, 9H 2C, 9H 6H 9H 2C, 8G 10E 2C, 9H 4C, 9G 7G 9H 9G 10E     Compound 6      ##STR309##      0.05 5C, 9H 9H 1G 5C, 9H 2C, 7H 5C, 9H 2C, 5G 2C 9G 8H 2C, 5H 7G     Compound 7      ##STR310##      0.05 10H 3C, 9H 3C, 8H 10H 6C, 9H 10E 3C, 9H 2C, 9G 9C 9H 9G 10E 10C     Compound 8      ##STR311##      0.05 10H 10H 9H 9C 9C 10E 6C, 9H 6C, 9G 9C 9H 9C 10E 10E  Compound 9      ##STR312##      0.05 10H 5C, 9H 9H 6C, 9H 6C, 9G 10E 5C, 9H 5C, 9H 9C 9H 9C 10E 10E     Compound 10      ##STR313##      0.05 2C, 5H 8G 0 6G 0 8G 0 0 2C, 2H 8H 0 0 4G      Compound 11     ##STR314##      0.05 5C, 9H 6C, 9H 2C, 2H, 5G 3C, 9G 3C, 9G 10E 3C, 8H 1C 9C 9H 8G 5G     2C, 8G      Compound 12     ##STR315##      0.05 6C, 9H 3C, 9G 1C, 1H 3C, 9G 3C, 9G 10E 7H 0 8H 8H 8H 0 8G     Compound 13      ##STR316##      0.05 3C, 7H 2C, 6H 0 0 2G 2C, 8G 2G 2G 2C 7H 0 3G 8G  Compound 14      ##STR317##      0.05 7C, 9H 10H 8H 3C, 9H 5C, 9H 10E 3C, 9H 3C, 7G 9G 9H 3C, 9G 10E 10C      Compound 15     ##STR318##      0.05 9H 4C, 9G 8H 3C, 9G 4C, 9H 10E 5C, 9H 5C, 8G 9H 9H 9G 10E 10E     Compound 16      ##STR319##      0.05 0 0 0 0 0 0 0 0 0 0 0 0 0  Compound 17      ##STR320##      0.05 5C, 9H 2C, 9G 1C 2C, 8G 6G 10E 8H 0 2C 8H 0 0 1H  Compound 18      ##STR321##       .05 3C, 9H 3C, 9G 0 2C, 9G 2C, 9H 10E 3H 1C 3H, 2C 3H 0 5G 7G     Compound 19      ##STR322##       .5 10H 9G 3C, 7H 3C, 8G 3C, 8G 10E 4C, 9H 2C 9G 9H 3C, 9G 10E 4C, 9G     Compound 20      ##STR323##       .5 10E 10E 9H 6C, 9H 6C, 9H 10E 6C, 9H 6C, 9G 9G 9H 9G 10E --     Compound 21      ##STR324##       .5 10E 10E 9H 10E 6C, 9H 10E 6C, 9H 6C, 9G 9C 9H 2C, 9G 10E --     Compound 22      ##STR325##       .5 2C, 8G 2C, 5G 0 5G 0 2C, 5G 2C 0 1C -- 1C 3G --  Compound 23      ##STR326##       .5 10H 2C, 9H 2G 2C, 9G 3C, 9H 10E 3C, 9H 5G 9G 9H 9G 7G --  Compound     24      ##STR327##       .5 6C, 9H 9H 4H 2C, 9G 2C, 9G 10E 2C, 9H 2C, 5G 2C, 8G 8H 9G 3G --     Compound 25      ##STR328##       .05 2C, 9G 3C, 7G 0 2C, 8G 2C, 5G 4C, 9H 3C, 7G 3C 0 8H 0 1C, 6G --     Compound 26      ##STR329##       .05 5C, 9H 2C, 8G 1C, 1H 8H 3C, 7G 10E 2C, 3G 1C, 6G 5G -- 9G 10E     --

Test B

Two plastic bulb pans were filled with fertilized and limed Woodstownsandy loam. One pan was planted with corn, sorghum, Kentucky bluegrassand several grassy weeds. The other pan was planted with cotton,soybeans, purple nutsedge (Cyperus rotundus), and several broadleafweeds. The following grassy and broadleaf weeds were planted: crabgrass(Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wildoats (Avena fatus), johnsongrass (Sorghum halepense), dallisgrass(Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass(Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthiumpensylvanicum), pigweed (Amaranthus retroflexus), morningglory (Ipomoeahederacea), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa),velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A12.5 cm diameter plastic pot was also filled with prepared soil andplanted with rice and wheat. Another 12.5 cm pot was planted withsugarbeets. The above four containers were treated preemergence withseveral test compounds within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B. Note that the compounds are highly active herbicides.

                                      TABLE B                                     __________________________________________________________________________    PRE-EMERGENCE ON                                                              WOODSTOWN SANDY LOAM                                                                 Compound 2                                                                            Compound 20     Compound 21     Compound                                                                              Compound 25            Rate kg/ha                                                                           .015                                                                              .060                                                                              .007                                                                              .015                                                                              .030                                                                              .120                                                                              .007                                                                              .015                                                                              .030                                                                              .120                                                                              .030                                                                              .120                                                                              .030                                                                              .120               __________________________________________________________________________    Crabgrass                                                                            5G  8G  8G, 8C                                                                            9G, 9C                                                                            10C 10C 5G  7G, 3H                                                                            10C 10C 0   0   6G  8G                 Barnyard-                                                                            7G, 3H                                                                            8G, 5C                                                                            8G, 5H                                                                            8G, 5H                                                                            9G, 9C                                                                            10C 6G  7G  7G, 8C                                                                            10C 0   2G  3G  2H, 5G             grass                                                                         Sorghum                                                                              10C 10C 10C 10C 10C 10E 10C 10C 10E 10C 7G, 5H                                                                            8G, 6C                                                                            2G  9G, 9C             Wild Oats                                                                            7G, 3C                                                                            7G, 3C                                                                            7G  8G, 3C                                                                            7G, 9C                                                                            10C 6G  6G  6G, 4C                                                                            7G, 8C                                                                            2G  6G, 5H                                                                            0   2G                 Johnsongrass                                                                         8G, 3H                                                                            8G, 5H                                                                            9G, 9C                                                                            9G, 9C                                                                            10C 10C 8G, 3H                                                                            9G, 9C                                                                            8G, 5H                                                                            10C 2G, 5H                                                                            7G, 5H                                                                            8G  9G                 Dallisgrass                                                                          0   5G  8G  8G, 3H                                                                            8G, 3H                                                                            9G, 9C                                                                            2G  4G  6G  9G, 9C                                                                            0   0   0   4G                 Giant foxtail                                                                        6G, 3H                                                                            9G, 9C                                                                            8G, 5H                                                                            10C 10C 10C 6G  10C 10C 10C 0   0   0   0                  Ky. bluegrass                                                                        7G  9G, 9C                                                                            7G, 5C                                                                            8G, 9C                                                                            10C 10C 5G  7G, 5C                                                                            10C 10C --  --  0   5G                 Cheatgrass                                                                           9G  9G  10C 10C 10C 10C 10E 10E 10E 10E 0   5G  0   3G                 Sugarbeets                                                                           8G  9G  7G, 8C                                                                            10C 10C 10C 6G, 5C                                                                            8G, 8C                                                                            9G, 9C                                                                            10C 3G  7G  0   5G                 Corn   8G, 7H                                                                            9G, 9C                                                                            6G, 5H                                                                            8G, 5H                                                                            9G, 9C                                                                            10C 4G  7G, 5H                                                                            8G, 5C                                                                            9G, 8C                                                                            0   9G, 9C                                                                            0   3G                 Mustard                                                                              9G  9G  9G, 8C                                                                            9G, 8C                                                                            10C 10C 9G, 6C                                                                            10C 10C 10C 0   0   0   2G                 Cocklebur                                                                            6G  6G  8G, 3H                                                                            8G, 5H                                                                            8G, 5H                                                                            9G, 8C                                                                            5G  6G  7G, 3H                                                                            8G, 3H                                                                            0   5G  0   2G                 Pigweed                                                                              --  --  8G, 9C                                                                            10E 10C 10E 8G, 8C                                                                            8G, 8C                                                                            10E 9G, 9C                                                                            --  --  --  --                 Nutsedge                                                                             10C 10C 8G  10E 9G  10E 4G  8G  8G  10E 2G  4G  4G  4G                 Cotton 3G  6G  5G  9G  8G, 3H                                                                            9G, 9C                                                                            2G  5G, 5H                                                                            8G, 5H                                                                            9G, 5C                                                                            0   5G, 3H                                                                            0   0                  Morningglory                                                                         3G  5G  5G  6G, 5H                                                                            7G  9G, 3C                                                                            4G  8G, 5H                                                                            6G  9G, 5C                                                                            0   4G  0   0                  Sicklepod                                                                            10C 8G  4G  8G  9G, 3C                                                                            9G, 7C                                                                            4G  5G  7G  9G, 5C                                                                            0   2G  0   0                  Teaweed                                                                              --  --  3G  7G, 3H                                                                            8G, 5C                                                                            9G, 9C                                                                            0   2G  5G  8G, 5C                                                                            0   0   2G  2G                 Velvetleaf                                                                           8G  9G  5G, 5H                                                                            8G, 5H                                                                            9G, 9C                                                                            10C 3G  6G, 5H                                                                            8G, 5H                                                                            10C 0   0   --  9G                 Jimsonweed                                                                           8G, 8C                                                                            9G, 9C                                                                            8G, 3C                                                                            10C 10C 9G, 9C                                                                            6G  8G, 3H                                                                            8G, 5C                                                                            9G, 9C                                                                            0   0   0   2G                 Soybean                                                                              5G  8G  0   6G, 5H                                                                            6G  9G, 8C                                                                            0   5G, 5H                                                                            6G, 5H                                                                            8G, 5H                                                                            0   5G  0   2G                 Rice   10C 10C 10E 10E 10C 10E 10E 10E 10E 10E 10C 10C 6G  10C                Wheat  6G  7G  6G  8G, 7C                                                                            6G, 3C                                                                            7G, 8C                                                                            7G  8G, 7C                                                                            6G, 3C                                                                            10C 0   0   0   2G                 __________________________________________________________________________

What is claimed is:
 1. A compound of the formula: ##STR330## wherein Ris C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₂ -C₄ alkoxyalkyl, C₅ -C₆ cycloalkyl,R¹ OCH₂ CH₂ OCH₂, R¹ OCH₂ CH₂ OCH₂ CH₂, ##STR331## CF₃, CF₃ CH₂ orHGLCCF₂, HCF₂ R¹ is methyl or ethyl;R² and R₃ are independently H, Cl,OCH₃, F, CH₃, Br, NO₂ or CF₃ ; n is 0, 1 or 2; G is F, Cl, Br or CF₃ ; Lis F, Cl or H; Z is H, F, Cl, Br, CH₃, CH₃ O or CH₃ S; W is O or S:##STR332## X is CH₃, CH₃ O or Cl; Y is CH₃, CH₃ CH₂, CH₃ O, CH₃ CH₂ O,CH₃ O(CH₂)_(m), CH₃ OCH₂ CH₂ O, R⁴ O₂ CR⁵ CHO, (CH₃)₂ N, CH₃ (CH₂ CN)N,NHCH₃ or NH₂ ; E is N; R⁴ is H, CH₃ or CH₃ CH₂ ; R⁵ is H or CH₃ ; R⁶ isH or CH₃ ; m is 1 or 2;and their agriculturally suitable salts; providedthat: (1) when W=S, then R⁶ is H; and (2) when X=Cl, then E=CH andY=CH₃, C₂ H₅, CH₃ O, C₂ H₅ O, CH₃ O(CH₂)_(m) --, NH₂, NHCH₃ or N(CH₃)₂.2. Compounds of claim 1 whereR is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₂ -C₄alkoxyalkyl, C₅ -C₆ cycloalkyl, R¹ OCH₂ CH₂ OCH₂, R¹ OCH₂ CH₂ OCH₂ CH₂,##STR333## CF₃, CF₃ CH₂ or HGLCCF₂ ; R¹ is methyl or ethyl; R² and R³are independently H, Cl, OCH₃, F, CH₃, Br, NO₂ or CF₃ ; n is 0, 1 or 2;G is F, Cl, Br or CF₃ ; L is F, Cl or H; Z is H, F, Cl, Br, CH₃, CH₃ Oor CH₃ S; W is O or S; ##STR334## X is CH₃ or CH₃ O; Y is CH₃, CH₃ CH₂,CH₃ O, CH₃ CH₂ O, CF₃ CH₂ O, CH₃ O(CH₂)_(m), CH₃ OCH₂ CH₂ O, R⁴ O₂ CR⁵CHO, (CH₃)₂ N or CH₃ (CH₂ CN)N; E is N; R⁴ is H, CH₃ or CH₃ CH₂ ; R⁵ isH or CH₃ ; R⁶ is H; m is 1 or 2;and their agriculturally suitable salts.3. Compounds of claim 1 or claim 2 wherein the substituent RSO₂ is atthe 2-position of the pyridine ring.
 4. Compounds of claim 3 wherein Wis O.
 5. Compounds of claim 4 wherein Z is H.
 6. Compounds of claim 5wherein R is C₁ -C₄ alkyl.
 7. Compounds of claim 6 wherein Y is CH₃, CH₃O or CH₃ CH₂ O.
 8. The compound of claim 1,N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.9. The compound of claim 1,N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.10. The compound of claim 1,N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.11. The compound of claim 1,N-[(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.12. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 1and at least one of the following: surfactant, solid or liquid diluent.13. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 2and at least one of the following: surfactant, solid or liquid diluent.14. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 3and at least one of the following: surfactant, solid or liquid diluent.15. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 4and at least one of the following: surfactant, solid or liquid diluent.16. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 5and at least one of the following: surfactant, solid or liquid diluent.17. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 6and at least one of the following: surfactant, solid or liquid diluent.18. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 1. 19. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 20. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 21. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 4. 22. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 5. 23. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim6.